CN105536863B - A kind of molecular sieve catalyst and its preparation method and purposes for methanol conversion for preparing arene - Google Patents
A kind of molecular sieve catalyst and its preparation method and purposes for methanol conversion for preparing arene Download PDFInfo
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Abstract
The present invention provides a kind of molecular sieve catalysts for methanol conversion for preparing arene, and it includes 5 molecular sieves of Hydrogen ZSM of 30 70 mass parts, the adhesives of the h-mordenite and 10 30 mass parts of the hydro-thermal process of 5 30 mass parts；Wherein, the molecular sieve catalyst also includes the metallic element being supported on 5 molecular sieves of Hydrogen ZSM and the nonmetalloid being supported on the h-mordenite of the hydro-thermal process；Wherein, the metallic element is one or more in Zn, Ag, Cd, Ga, Co, Mo, Cr, La and Ce, its load capacity is 0.5 10 mass parts in terms of metallic element quality, and the nonmetalloid is one or more in P, F and B, load capacity is 0.1 5 mass parts in terms of nonmetalloid quality.The present invention also provides the preparation method of the catalyst and the applications in the reaction of preparing aromatic hydrocarbon through methanol transformation.The catalyst can effectively optimize product distribution, improve the economic operation level of MTA commercial plants.
Description
Technical field
The invention belongs to catalyst technical fields, and more particularly to a kind of molecular sieve for methanol conversion for preparing arene
The preparation method and purposes of catalyst and this catalyst.
Background technology
Aromatic hydrocarbons includes mainly benzene, toluene and dimethylbenzene (being commonly abbreviated as " BTX "), is important basic chemical industry raw material.It passes
The aromatics production of system, other than by-product crude benzol and coal tar of the small part in coking industry, about 90% depends on stone
The petrochemical processings such as oily catalytic reforming and Pintsch process ethylene.Due to the energy distribution situation of China's " rich coal, oil-poor, few gas ",
The technical research and exploitation of methanol conversion for preparing arene (MTA) are not only that coal conversion for preparing arene opens a new technology road
Line, also the methanol production capacity for China's surplus finds a practicable outlet, but also can meet market to the huge of aromatic hydrocarbons
Big demand constantly reduces degree of dependence of the aromatics production to petroleum resources.
The key of MTA technologies is efficient aromatization of methanol catalyst, and research at present focuses mainly on how improving liquid phase
The selectivity of the yield and aromatic hydrocarbons (BTX) of product.In BTX products, mixed xylenes (Xylene) is as important foundation stone
Change raw material, is widely used for medicine, fragrance and dyestuff intermediate raw material.Wherein, ortho-xylene (OX) is mainly for the production of phthalic anhydride,
It is important the raw material of plasticizer (such as DOP, DBP)；Meta-xylene (MX) can be used as manufacturing the raw material of M-phthalic acid；And it is right
Dimethylbenzene (PX) is the primary raw material of terylene and polyester resin.Consider from economic benefit angle, efficient MTA catalyst should have
The selectivity and yield of high mixed xylenes.
Currently, ZSM-5 molecular sieve is main MTA catalyst, and may be used metal-modified or nonmetallic modifying.
ZSM-5 molecular sieve belongs to rhombic system, the duct that intersects with size uniform, a kind of straight tube shape for ellipsoidal cross section
Duct (pore size be 0.54nm × 0.56nm), another kind are that section is approximately that (pore size is in circular Z-shaped duct
0.52nm×0.58nm)。
Chinese patent application CN104801332A discloses a kind of Hydrogen ZSM-5 molecules that the Co for MTA reactions is modified
Sieve catalyst.Chinese patent application CN103028436A discloses a kind of catalyst of methanol aromatic hydrocarbons, use ZSM-5,
ZSM-11, H β or HY as sieve component, using at least one of copper, zinc, silver, cadmium element or its oxide and gallium or
At least one of lanthanum element or its oxide are modified, Al2O3Or SiO2At least one of be used as binder, the catalysis
Agent is in 390 DEG C, WHSV=2.0h-1And the BTX yields under normal pressure are 35%.
In addition, with industrial expansions such as China's polyester, it is contemplated that the demand of BTX will continue to grow at top speed.Although existing skill
Methanol is converted to yield and the selectivity of the aromatics yield of aromatic hydrocarbons method, BTX and is increased in art, but diformazan in BTX products
The yield of benzol mixture is still relatively low.
Therefore, it needs exist for providing the molecular sieve catalyst for methanol conversion for preparing arene, to improve MTA techniques
Economy improves mixed xylenes in BTX products especially while improving the aromatics yield and BTX yields of catalyst
Yield.
Invention content
Therefore, it is an object of the present invention to provide a kind of molecular sieve catalyst for methanol conversion for preparing arene, this is urged
Agent has high aromatics yield and BTX yields, while having high mixed xylenes yield.Another object of the present invention is
The preparation method and purposes of the molecular sieve catalyst are provided.
The purpose of the present invention is what is be achieved through the following technical solutions.
On the one hand, the present invention provides a kind of molecular sieve catalyst for methanol conversion for preparing arene, the molecular sieve is urged
Agent include the Hydrogen ZSM-5 molecular sieves of 30-70 mass parts, 5-30 mass parts hydro-thermal process h-mordenite and 10-
The adhesive of 30 mass parts；Wherein, the molecular sieve catalyst also includes the metal being supported on the Hydrogen ZSM-5 molecular sieve
Element and the nonmetalloid being supported on the h-mordenite of the hydro-thermal process；Wherein, the metallic element be selected from Zn,
One or more in Ag, Cd, Ga, Co, Mo, Cr, La and Ce, load capacity is the 0.5-10 mass in terms of metallic element quality
Part and the nonmetalloid are one or more in P, F and B, and load capacity is in terms of nonmetalloid quality
0.1-5 mass parts.
According to molecular sieve catalyst provided by the invention, wherein the silica alumina ratio of the Hydrogen ZSM-5 molecular sieve is
20-200, preferably 20-100.
As used herein, term " silica alumina ratio " (silica alumina molar ratio, SAR) is general
It refer to the molar ratio of element silicon and aluminium element in material such as molecular sieve.
According to molecular sieve catalyst provided by the invention, wherein mordenite (MOR) molecular sieve category rhombic system, reason
The structure cell thought forms：Na8(Al8Si40O96)·24H2O, pore passage structure areHydrogen suitable for the present invention
The silica alumina ratio of modenite is preferably 20-50.
In some embodiments, the silica alumina ratio of the h-mordenite is 5-50, and in some embodiment party
The silica alumina ratio of h-mordenite described in case is 20-50.
According to molecular sieve catalyst provided by the invention, wherein the load capacity of the metallic element is with metallic element matter
Gauge 0.5-5 mass parts and the load capacity of the nonmetalloid are the 0.1-2 mass parts in terms of nonmetalloid quality.
According to molecular sieve catalyst provided by the invention, wherein described adhesive is selected from activated alumina, intends thin water aluminium
It is one or more in stone, kaolin and clay.
On the other hand, the present invention provides the method for preparing the molecular sieve catalyst, the method includes：Load is had
The Hydrogen ZSM-5 molecular sieve of metallic element, load have the h-mordenite that the hydro-thermal process of nonmetalloid crosses, adhesive,
Pore structure conditioning agent, extrusion aid and peptizing agent mixing, extruded moulding is dry, is then forged at 500-700 DEG C in air atmosphere
It burns, to which molecular sieve catalyst be made.
According to method provided by the invention, wherein it is to pass through packet that the load, which has the Hydrogen ZSM-5 molecular sieve of metallic element,
Prepared by the method for including following steps：Using metallic element soluble compound aqueous solution to Hydrogen ZSM-5 molecular sieve into
Row dipping, is then dried, and is roasted such as 5-10 hours in 500-550 DEG C.
In the present invention, method as known in the art may be used, Hydrogen ZSM-5 molecular sieve is impregnated, for example, yellow
Written by Zhong Tao, Geng Jianming《Industrial Catalysis》(second edition), Beijing：Chemical Industry Press, the incipient impregnation described in 2006
Method.
In some embodiments, Hydrogen ZSM-5 molecular sieve is impregnated using equi-volume impregnating, the time of dipping
It is 8-12 hours.
According to method provided by the invention, wherein the soluble compound of the metallic element is the nitric acid of metallic element
Salt, sulfate or chlorate etc..
In the present invention, the aqueous solution of the soluble compound of the metallic element is by by the solubilityization of metallic element
It closes object and is dissolved in and prepare in deionized water.
According to method provided by the invention, wherein the Hydrogen mercerising boiling for loading the hydro-thermal process for having nonmetalloid
Stone is prepared by method comprising the following steps：
(1) vapor and N are used at 400-700 DEG C2Mixed gas such as 4- is handled to h-mordenite
10 hours, obtain the h-mordenite of hydro-thermal process；With
(2) use the aqueous solution of the soluble compound of nonmetalloid to the h-mordenite of the hydro-thermal process into
Row dipping, is then dried, and in 400-450 DEG C of roasting.
In some embodiments, vapor and N in step (1)2Mixed gas in vapor content be 20-
70%, it is in some embodiments 30-50%, and be 35% in some embodiments.
In some embodiments, vapor and N in step (1)2Mixed gas be to the processing of h-mordenite
At 450-650 DEG C, such as carried out at 600 DEG C, the time is preferably 5-8 hours.
Likewise it is possible to carry out dipping example to the h-mordenite of hydro-thermal process using method as known in the art
Such as, written by Huang Zhongtao, Geng Jianming《Industrial Catalysis》(second edition), Beijing：Chemical Industry Press, it is isometric described in 2006
Infusion process.In some embodiments, the h-mordenite of the hydro-thermal process is impregnated using equi-volume impregnating,
The time of dipping is 8-12 hours.
In some embodiments, the soluble compound of nonmetalloid described in step (2) be ammonium fluoride, phosphoric acid,
Ammonium phosphate, boric acid or ammonium borate etc..
In some embodiments, the aqueous solution of the soluble compound of nonmetalloid described in step (2) is to pass through
The soluble compound of nonmetalloid is dissolved in and is prepared in deionized water.
According to method provided by the invention, wherein the temperature of the calcining is 550-650 DEG C.
According to method provided by the invention, wherein the time of the calcining is 5-10 hours, preferably 5-7 hours, more excellent
It is selected as 5-6 hours.
In some embodiments, calcining 5-7 is small at 500-700 DEG C in air atmosphere for dry extruded moulding product
When；And it in some embodiments, is calcined 5-6 hours at 550-650 DEG C in air atmosphere.
In some embodiments, it the described method comprises the following steps：
(1) it uses the aqueous solution of the soluble compound of metallic element to impregnate Hydrogen ZSM-5 molecular sieve, then does
It is dry, and in 500-550 DEG C of roasting, have the Hydrogen ZSM-5 molecular sieve of metallic element to which load be made；
(2) vapor and N are used at 400-700 DEG C2Mixed gas h-mordenite is handled, obtain water
The h-mordenite of heat treatment；
(3) use the aqueous solution of the soluble compound of nonmetalloid to the h-mordenite of the hydro-thermal process into
Row dipping, is then dried, and in 400-450 DEG C of roasting, to which the Hydrogen silk that load has the hydro-thermal process of nonmetalloid be made
Geolyte；With
(4) load of Hydrogen ZSM-5 molecular sieve, step (3) preparation that metallic element prepared by step (1) is modified is had non-
H-mordenite, adhesive, pore structure conditioning agent, extrusion aid and the peptizing agent mixed-forming of the hydro-thermal process of metallic element,
It is dry, it is then calcined at 500-700 DEG C in air atmosphere, to which molecular sieve catalyst be made.
According to method provided by the invention, wherein the pore structure conditioning agent is selected from methylcellulose, starch, polyethylene
One or more in alcohol, polyethylene glycol, sucrose and glucose, dosage is the 5-20% of molecular sieve catalyst quality.
According to method provided by the invention, wherein the extrusion aid is selected from graphite powder, sesbania powder, oxalic acid, citric acid, sweet
One or more in oil and stearic acid, dosage is the 1-5% of molecular sieve catalyst quality.
According to method provided by the invention, wherein the peptizing agent is selected from nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, acetic acid
With it is one or more in malonic acid.
In preferred embodiments, the peptizing agent be solution form, a concentration of 10-30% of the solution, and
Load has the Hydrogen ZSM-5 molecular sieve of metallic element, loads the h-mordenite for the hydro-thermal process for having nonmetalloid and glue
Mixture gross mass and the ratio of peptizing agent liquor capacity are 1:1-1.5g/ml.
In the present invention, there is no particular/special requirement to the temperature of the drying process in each step.In some embodiments, it impregnates
The drying temperature of the h-mordenite of the hydro-thermal process after Hydrogen ZSM-5 molecular sieve and dipping afterwards is each independently 80-
120 DEG C, preferably 100-120 DEG C.
In some embodiments, load has the water that the Hydrogen ZSM-5 molecular sieve of metallic element, load have nonmetalloid
The h-mordenite of heat treatment, adhesive, pore structure conditioning agent, extrusion aid and peptizing agent mixture after extruded moulding
Temperature in drying process is 50-120 DEG C, preferably 70-100 DEG C, for example, 80 DEG C.
In another aspect, the present invention provides a kind of molecular sieve catalyst for methanol conversion for preparing arene, the catalyst
It is prepared by the above method.
Another aspect, the present invention also provides the molecular sieve catalyst answering in the reaction of preparing aromatic hydrocarbon through methanol transformation
With.
Molecular sieve catalyst provided by the invention has at least the following advantages：
(1) catalyst of the invention can improve aromatics yield and BTX yields in product, while have highly selective mixing
Dimethylbenzene.
(2) ZSM-5 molecular sieve that the present invention is modified using metallic element has non-gold as the first active component using load
Belong to the modenite of the hydro-thermal process of element as the second active component, adhesive is added and is prepared for being used for methanol conversion for preparing arene
Molecular sieve catalyst.It is not intended to be restricted by theory, it is believed that molecular sieve catalyst of the invention can overcome due to its two dimension pipe
Beam hole road be easy block inactivation and cause modenite easily coking the shortcomings that.
(3) compared with prior art, catalyst of the invention uses the molecular sieve of two kinds of different function as activearm
Point, and acid and pore passage structure modification has not been carried out for different component in catalyst so that in MTA reaction process, respectively
Main side effect realizes best coupling and synergistic effect on a catalyst.Catalyst using the present invention can be converted in methanol
During aromatic hydrocarbons processed, aromatic hydrocarbons high in product and BTX yields are realized, and improves the yield of mixed xylenes.Therefore, should
Catalyst is applied in MTA techniques, can effectively optimize product distribution, improves the economic operation level of MTA commercial plants.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein：
Fig. 1 is that the methanol conversion of the catalyst and the catalyst of comparative example 2,3 of the embodiment of the present invention 1 changes with time
Curve.
Specific implementation mode
Present invention will be further explained below with reference to specific examples, but these embodiments are only limitted to explain the present invention, without
For limiting the present invention.
The experimental method for the specific experiment condition being not specified in following example, usually according to normal condition, or according to factory
Condition proposed by quotient, the in the examples below variation of technical solution are within the scope of the invention.
Embodiment 1
The present embodiment is for illustrating molecular sieve catalyst of methanol conversion for preparing arene and preparation method thereof.Specifically, molecule
The preparation method of sieve catalyst includes the following steps：
(1) modification of Hydrogen ZSM-5 molecular sieve：
Weigh 5.0g Zn (NO3)2·6H2O is dissolved in wiring solution-forming in 20mL deionized waters, is then added into the solution
The Hydrogen ZSM-5 molecular sieve (Shanghai Zhuoyue Chemical Science Co., Ltd's production) that 20g silica alumina ratios are 30, at room temperature impregnation
10 hours.Hydrogen ZSM-5 molecular sieve after impregnation is dried at 120 DEG C, is then roasted 5 hours at 550 DEG C, to
Obtaining load has the Hydrogen ZSM-5 molecular sieve of Zn elements.
(2) modification of h-mordenite：
H-mordenite (Shanghai Fuxu Molecular Sieve Co., Ltd.'s production) sample that 10.0g silica alumina ratios are 10 is weighed to be placed in
In tube furnace, it is passed through the H that volume ratio is 35/652O/N2Mixed gas handles 6 hours at 600 DEG C, then makes sample in N2Gas
It is cooled to room temperature in atmosphere, obtains the modenite of hydro-thermal process.
Weigh 1.0g NH4F is dissolved in wiring solution-forming in 10mL deionized waters, and the silk after hydro-thermal is then added into the solution
Geolyte, at room temperature impregnation 10 hours.Modenite after impregnation is dried at 120 DEG C, then at 550 DEG C
Roasting 5 hours, obtaining load has the h-mordenite of hydro-thermal process of F elements.
(3) roasting prepares molecular sieve catalyst：
Weighing step (1) load obtained has the load obtained of the Hydrogen ZSM-5 molecular sieve 21.0g of Zn elements, step (2)
There are the h-mordenite 10.5g, activated alumina (adhesive) 10.0g, sesbania powder (extrusion aid) of the hydro-thermal process of F elements
The nitric acid that the mass percentage of 45.0mL is 25% is added after mixing in 1.0g and starch (pore structure conditioning agent) 4.5g
Solution (peptizing agent), extruded moulding are dried at 80 DEG C, and are roasted 5 hours at 550 DEG C, to obtain final catalyst.
Embodiment 2-8
With reference to embodiment 1, prepares and be used for methanol conversion for preparing arene, different component molecular sieve catalyst.Embodiment 2-8
Molecular sieve catalyst prepare raw material and partial condition is as shown in table 1.In addition, in the modification procedure of h-mordenite,
The gas being passed through is the H that volume ratio is 30/702O/N2Mixed gas, and correspondingly use NH4F, ammonium phosphate and ammonium borate；With
And in the calcination steps of molecular sieve catalyst, after extruded moulding, dry at 100 DEG C, and is roasted 5 hours at 600 DEG C, from
And obtain final catalyst.
Comparative example 1
Preparing load has the ZMS-5 molecular sieve catalysts of Zn elements, specifically includes the following steps：
Weigh 10.0g Zn (NO3)2·6H2O is dissolved in wiring solution-forming in 40mL deionized waters, is then added into the solution
It is small to impregnate 10 at room temperature for the Hydrogen ZSM-5 molecular sieve (Shanghai Zhuoyue Chemical Science Co., Ltd's production) that 40g silica alumina ratios are 30
When.Hydrogen ZSM-5 molecular sieve after impregnation is dried at 120 DEG C, is then roasted 5 hours at 550 DEG C, to obtain
Load has the Hydrogen ZSM-5 molecular sieve of Zn elements.
Weigh Hydrogen ZSM-5 molecular sieve 31.5g, the activated alumina (adhesive) obtained above for loading and there are Zn elements
10.0g, sesbania powder extrusion aid) quality hundred of 45.0mL is added after mixing in 1.0g and starch (pore structure conditioning agent) 4.5g
It is 25% salpeter solution (peptizing agent) to divide content, and extruded moulding is dried at 80 DEG C, and is roasted 5 hours at 550 DEG C, is obtained
There are the ZMS-5 molecular sieve catalysts of Zn elements to load.
Comparative example 2
By without H2O/N2The h-mordenite of hydro-thermal process prepares molecular sieve catalyst.Specifically, molecular sieve catalyst
Preparation method include the following steps：
(1) modification of Hydrogen ZSM-5 molecular sieve：
Weigh 5.0g Zn (NO3)2·6H2O is dissolved in wiring solution-forming in 20mL deionized waters, is then added into the solution
The Hydrogen ZSM-5 molecular sieve (Shanghai Zhuoyue Chemical Science Co., Ltd's production) that 20g silica alumina ratios are 30, at room temperature impregnation
10 hours.Hydrogen ZSM-5 molecular sieve after impregnation is dried at 120 DEG C, is then roasted 5 hours at 550 DEG C, to
Obtaining load has the Hydrogen ZSM-5 molecular sieve of Zn elements.
(2) modification of h-mordenite：
Weigh 1.0g NH4F is dissolved in wiring solution-forming in 10mL deionized waters, and 10.0g silica alumina ratios are then added into the solution
For 10 h-mordenite (Shanghai Fuxu Molecular Sieve Co., Ltd.'s production) sample, impregnation 10 hours at room temperature.It will
Modenite after impregnation is dried at 120 DEG C, is then roasted 5 hours at 550 DEG C, and obtaining load has the hydrogen of F elements
Type modenite.
(3) roasting prepares molecular sieve catalyst：
Weighing step (1) load obtained has the load obtained of the Hydrogen ZSM-5 molecular sieve 21.0g of Zn elements, step (2)
There are h-mordenite 10.5g, activated alumina (adhesive) 10.0g, sesbania powder (extrusion aid) 1.0g and the starch of F elements
Salpeter solution (the peptization that the mass percentage of 45.0mL is 25% is added after mixing in (pore structure conditioning agent) 4.5g
Agent), extruded moulding is dried at 80 DEG C, and is roasted 5 hours at 550 DEG C, to obtain final catalyst.
Comparative example 3
Molecular sieve catalyst is prepared by the h-mordenite of non-modified processing.Specifically, the system of molecular sieve catalyst
Preparation Method includes the following steps：
(1) modification of Hydrogen ZSM-5 molecular sieve：
Weigh 5.0g Zn (NO3)2·6H2O is dissolved in wiring solution-forming in 20mL deionized waters, is then added into the solution
The Hydrogen ZSM-5 molecular sieve (Shanghai Zhuoyue Chemical Science Co., Ltd's production) that 20g silica alumina ratios are 30, at room temperature impregnation
10 hours.Hydrogen ZSM-5 molecular sieve after impregnation is dried at 120 DEG C, is then roasted 5 hours at 550 DEG C, to
Obtaining load has the Hydrogen ZSM-5 molecular sieve of Zn elements.
(2) roasting prepares molecular sieve catalyst：
Weighing step (1) load obtained has Hydrogen ZSM-5 molecular sieve 21.0g, the h-mordenite (Shanghai of Zn elements
Fu Xu molecular sieves Co., Ltd produces) 10.5g, activated alumina (adhesive) 10.0g, sesbania powder (extrusion aid) 1.0g and starch
Salpeter solution (the peptization that the mass percentage of 45.0mL is 25% is added after mixing in (pore structure conditioning agent) 4.5g
Agent), extruded moulding is dried at 80 DEG C, and is roasted 5 hours at 550 DEG C, to obtain final catalyst.
Comparative example 4
Preparing load has the h-mordenite of F elements.Specifically, include the following steps：
(1) h-mordenite (Shanghai Fuxu Molecular Sieve Co., Ltd.'s production) sample that 30.0g silica alumina ratios are 10 is weighed
It is placed in tube furnace, is passed through the H that volume ratio is 35/652O/N2Mixed gas handles 6 hours at 600 DEG C, then sample is made to exist
N2It is cooled to room temperature in atmosphere, obtains the modenite of hydro-thermal process.
(2) 3.0g NH are weighed4F is dissolved in wiring solution-forming in 30mL deionized waters, and hydro-thermal process then is added into the solution
Modenite, impregnation 10 hours at room temperature.Modenite after impregnation is dried at 120 DEG C, then 550
It is roasted 5 hours at DEG C, obtaining load has the h-mordenite of F elements.
(3) step (2) load obtained is had to h-mordenite 31.5g, the activated alumina (adhesive) of F elements
The quality of 45.0mL is added after mixing in 10.0g, sesbania powder (extrusion aid) 1.0g and starch (pore structure conditioning agent) 4.5g
The salpeter solution (peptizing agent) that percentage composition is 25%, extruded moulding is dried at 80 DEG C, and is roasted 5 hours at 550 DEG C,
To obtain final catalyst.
Catalytic performance test
Catalyst made from embodiment 1,3,5,8 and Comparative Examples 1 and 2,3 is catalyzed using flow reactor of fixed bed
Performance evaluation.The loaded catalyst evaluated every time is 3.0g, and using pure methanol as raw material, at 200 DEG C, pure methanol first passes around
Preheater equipped with inertia quartz sand carries out MTA reactions, liquid hourly space velocity (LHSV) 2h subsequently into main reactor- 1, reaction temperature is
420 DEG C, system stagnation pressure is less than 0.05MPa.The product of MTA can be divided into gas and water, oily three-phase, and product is after drainer cools down, gently
It is online that hydrocarbon (the various alkene and alkane of C1-C5) etc. is directly entered the gas-chromatography with HP-PLOT-Q columns as gas-phase product
Analysis；And liquid phase is then collected by cold-trap, is taken out after a certain period of time, by liquid phase separation is water phase and oil phase with separatory funnel,
It is mainly aromatic hydrocarbons in oil phase, using the gas-chromatography off-line analysis with DB-WAX columns；And methanol conversion<When 100%, water phase
In will contain unreacted methanol and a small amount of dimethyl ether, by the gas-chromatography off-line analysis with HP-PLOT-Q columns, wherein
Water phase and oil phase are analyzed using internal standard method.Gas and water, all products of oil indicate finally by normalization with carbon-based mass content,
Reaction result is listed in table 2.
The selectivity of product comparison of table 2, catalyst
Note：B indicates that benzene, T indicate that toluene, X indicate dimethylbenzene in table 2.
As can be known from the results of Table 2, it is 100% in methanol conversion, the catalyst of embodiment 1,3,5,8 is compared with
The catalyst of example 1,2,3,4 is compared, and catalyst produced by the present invention realizes high in product during methanol conversion for preparing arene
Aromatics yield and BTX yields, and realize the effect of voluminous mixed xylenes (X).
Anti-coking is evaluated
The methanol conversion versus time curve of the catalyst of embodiment 1 and the catalyst of comparative example 2,3 is determined,
Its condition and method can evaluate identical, the result is shown in Figure 1 with catalyst.
Embodiment 1 has carried out hydro-thermal process first to modenite, and it is element modified then to have carried out F, comparative example 2
It is element modified to have carried out F, and has not carried out hydro-thermal process in comparative example 3 and F is element modified.As shown in Figure 1, in same time,
The methanol conversion of the catalyst of embodiment 1 maintains 100%, and the methanol conversion of comparative example 2 and 3 catalyst is only preceding 2
A hour is 100%, is then quickly down to 90% hereinafter, this shows catalyst using the present invention in methanol conversion for preparing arene mistake
High anti-coking can be shown in journey.
Claims (29)
1. a kind of molecular sieve catalyst for methanol conversion for preparing arene, the molecular sieve catalyst includes 30-70 mass parts
Hydrogen ZSM-5 molecular sieve, 5-30 mass parts hydro-thermal process h-mordenite and 10-30 mass parts adhesive；Wherein,
The molecular sieve catalyst also includes the metallic element being supported on the Hydrogen ZSM-5 molecular sieve and is supported at the hydro-thermal
Nonmetalloid on the h-mordenite of reason；Wherein, the metallic element be selected from Zn, Ag, Cd, Ga, Co, Mo, Cr, La and
One or more in Ce, load capacity is 0.5-10 mass parts and nonmetalloid choosing in terms of metallic element quality
From one or more in P, F and B, load capacity is the 0.1-5 mass parts in terms of nonmetalloid quality.
2. molecular sieve catalyst according to claim 1, wherein the silica alumina ratio of the Hydrogen ZSM-5 molecular sieve is
20-200。
3. molecular sieve catalyst according to claim 1, wherein the silica alumina ratio of the Hydrogen ZSM-5 molecular sieve is
20-100。
4. molecular sieve catalyst according to claim 1, wherein the silica alumina ratio of the h-mordenite is 5-
50。
5. molecular sieve catalyst according to claim 1, wherein the silica alumina ratio of the h-mordenite is 20-
50。
6. molecular sieve catalyst according to any one of claim 1 to 5, wherein the load capacity of the metallic element is
0.5-5 mass parts and the load capacity of the nonmetalloid are the 0.1-2 in terms of nonmetalloid quality in terms of metallic element quality
Mass parts.
7. molecular sieve catalyst according to any one of claim 1 to 5, wherein described adhesive is selected from active oxidation
It is one or more in aluminium, boehmite and clay.
8. molecular sieve catalyst according to any one of claim 1 to 5, wherein described adhesive is kaolin.
9. the method for preparing molecular sieve catalyst described in any item of the claim 1 to 8, the method includes：Load is had
The Hydrogen ZSM-5 molecular sieve of metallic element, load have the h-mordenite, adhesive, hole of the hydro-thermal process of nonmetalloid
Structure regulator, extrusion aid and peptizing agent mixing, extruded moulding is dry, is then forged at 500-700 DEG C in air atmosphere
It burns, to which molecular sieve catalyst be made.
10. according to the method described in claim 9, wherein, it is to pass through that the load, which has the Hydrogen ZSM-5 molecular sieve of metallic element,
Prepared by method comprising the following steps：Using metallic element soluble compound aqueous solution to Hydrogen ZSM-5 molecular sieve
It is impregnated, is then dried, and in 500-550 DEG C of roasting.
11. according to the method described in claim 10, wherein, the time of the roasting is 5-10 hours.
12. according to the method described in claim 10, wherein, the soluble compound of the metallic element is the nitre of metallic element
Hydrochlorate, sulfate or chlorate.
13. according to the method described in claim 10, wherein, the dipping to Hydrogen ZSM-5 molecular sieve is to use incipient impregnation
What method carried out, the time of dipping is 8-12 hours.
14. the method according to any one of claim 9 to 13, wherein the load has at the hydro-thermal of nonmetalloid
The h-mordenite of reason is prepared by method comprising the following steps：
(1) vapor and N are used at 400-700 DEG C2Mixed gas h-mordenite is handled, obtain at hydro-thermal
The h-mordenite of reason；With
(2) aqueous solution of the soluble compound of nonmetalloid is used to soak the h-mordenite of the hydro-thermal process
Then stain is dried, and in 400-450 DEG C of roasting.
15. according to the method for claim 14, wherein the time handled described in step (1) is 4-10 hours.
16. according to the method for claim 14, wherein vapor and N in step (1)2Mixed gas in vapor contain
Amount is 20-70 volumes %.
17. according to the method for claim 14, wherein vapor and N in step (1)2Mixed gas in vapor contain
Amount is 30-50 volumes %.
18. according to the method for claim 14, wherein vapor and N in step (1)2Mixed gas to Hydrogen mercerising boil
The processing of stone carries out at 450-650 DEG C, and the time is 5-8 hours.
19. according to the method for claim 14, wherein the soluble compound of nonmetalloid described in step (2) is
Ammonium fluoride, phosphoric acid, ammonium phosphate, boric acid or ammonium borate.
20. according to the method for claim 14, wherein be in step (2) using equi-volume impregnating to the hydro-thermal at
What the h-mordenite of reason was impregnated, the time of dipping is 8-12 hours.
21. the method according to any one of claim 9 to 13, wherein the temperature of the calcining is 550-650 DEG C.
22. according to the method for claim 21, wherein the time of the calcining is 5-10 hours.
23. according to the method for claim 21, wherein the time of the calcining is 5-7 hours.
24. according to the method for claim 21, wherein the time of the calcining is 5-6 hours.
25. the method according to any one of claim 9 to 13, wherein the pore structure conditioning agent is selected from Methyl cellulose
One or more in element, starch, polyvinyl alcohol, polyethylene glycol, sucrose and glucose, dosage is molecular sieve catalyst quality
5-20%.
26. the method according to any one of claim 9 to 13, wherein the extrusion aid be selected from graphite powder, sesbania powder,
One or more in oxalic acid, citric acid, glycerine and stearic acid, dosage is the 1-5% of molecular sieve catalyst quality.
27. the method according to any one of claim 9 to 13, wherein the peptizing agent be selected from nitric acid, hydrochloric acid, phosphoric acid,
It is one or more in sulfuric acid, formic acid, acetic acid and malonic acid.
28. the method according to any one of claim 9 to 13, wherein the peptizing agent is the form of solution, the solution
A concentration of 10-30 mass %, and load the Hydrogen ZSM-5 molecular sieve for having metallic element, load has the water of nonmetalloid
The h-mordenite and adhesive gross mass and the ratio of peptizing agent liquor capacity of heat treatment are 1:1-1.5g/ml.
29. molecular sieve catalyst described in any item of the claim 1 to 8 answering in the reaction of preparing aromatic hydrocarbon through methanol transformation
With.
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| CN106622344A (en) * | 2016-12-06 | 2017-05-10 | 中国科学院山西煤炭化学研究所 | Metal-nonmetal modified catalyst and preparation method thereof |
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| WO2018197471A1 (en) * | 2017-04-24 | 2018-11-01 | Basf Se | Process for the conversion of methanol to p-xylene |
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| CN107469767B (en) * | 2017-09-14 | 2019-10-25 | 山东理工大学 | Silica/nano-titanium dioxide/silicone zeolite composite material of Treatment of Cyanide-containing Wastewater and its application |
| CN107866264B (en) * | 2017-11-21 | 2020-08-28 | 万华化学集团股份有限公司 | Catalyst for synthesizing DEMMA (DEMMA), and preparation method and application thereof |
| CN109970515B (en) * | 2019-03-04 | 2021-10-19 | 宝鸡文理学院 | Catalytic refining method of phenol in process of synthesizing anisole by methanol method |
| CN110652957B (en) * | 2019-11-14 | 2022-02-18 | 广州大学 | Preparation method and application of pseudo-boehmite microspheres |
| CN114453003B (en) * | 2020-10-21 | 2024-01-26 | 中国石油化工股份有限公司 | Aromatization catalyst and activity recovery method and application thereof |
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